Stabilization of regenerated cellulose fabric with glyoxal-amide reaction product



Patented July 31, 1951 STABILIZATION OF BEGENERA'IED CELLU- LOSE FABRIC WITH GLYOXAL-AMIDE REACTION PRODUCT Jack Epelberg, Cohoes, and Raymond E. Pemriek,

' UNITED STATES PATENT OFFICE Troy, N. Y., assignorl to Cluett, Peabody 8;. 00., Inc., Troy, N. Y., a corporation of New York No Drawing. Application February 6, 1948,

Serial No. 6,815

Claims. (Cl. 8-1163) 1 This invention relates to textile materials containing a substantial quantity of regenerated cellulose, and more particularly to the stabilization of such textile materials with respect to laundry shrinkage or progressive dimensional shrinkage.. The'term textile materials as used herein is intended to include filaments and fibers, staple or yarn, either in the finished stage or at some intermediate stage in the production thereof, and also to include fabrics whether knitted, woven or felted, as well as garments or other articles made from such-fabrics.

The invention is of particular importance with reference to fabrics made of yarns or threads containing substantial amounts of, or made entirely of regenerated cellulose. The fibers of regenerated cellulose have a considerable natural tendency to absorb water and swell, with the result that fabrics made therefrom are very unstable in dimensions when laundered. We have discovered that textile materials containing substantial quantities of, or which are formed predominantly or entirely of, regenerated cellulose may be stabilized against progressive dimensional shrinkage under repeated laundry washings and given substantial resistance to wrinkling, abrasion, crushing and creasing, by

reacting upon such materials with the reaction product of a dialdehyde known as glyoxal and an amide, which amide has the formula where R represents hydrogen or an alkyl radical having less than a 6 carbon atom primary chain, and suitably catalyzed with an acidic catalyst. This reaction is obtained by first wetting the textile materials with an aqueous solution containing this reaction product and the catalyst, then separating off the excess wetting solution, and then drying the wetted materials so freed of excess solution, at a temperature well above normal room temperature until approximate dryness has been obtained.

In accordance with this discovery, the reaction product of glyoxal and an amide is obtained by mixing molar quantities or fractions of molar 'quantities of the glyoxal and the amide, which react at room temperatures with vigorous stirring. The glyoxal is a dialdehyde having the structural formula HG=O and it is also sometimes referred to as oxalic 2 aldehyde or ethandial. It is at present commercially available only in an aqueous solution containing approximately 30% by weight of glyoxal, and this commercial glyoxal is decidedly acid with a pH between about 1.00 and 1.30. The reaction of this glyoxal with the amide may also take place at elevated temperatures, but the use which is an intermolecular dehydration rather than an additionreaction. The complex obtained by the reaction of the glyoxal and the amide, after being catalyzed and applied to the textile material, reacts with the cellulose of the material to form a very complex chain which is probably cross-linked throughout.

In attempting to use glyoxal and amides in stabilizing rayon fabrics, it was discovered that the reaction product has a potential color, which when applied to the textile materials serves to color or dye them. Therefore, there were two problems which had to be overcome, namely; (1) the discoloration evolved when glyoxal and elementary nitrogen combined to form .the basic chromofore group appearing as a yellowishbrown coloration on the fabric, and (2) tofind a catalyst which would give satisfactory shrinkage stabilization and at the same time would cause little or no damage to the textile material. We

found that the problem of discoloration and the selection of catalyst were definitely related.

The catalysts suitable for this purpose are the acidic catalysts having a substantial acidic component that is not eliminated when concentrated to approximate dryness at temperatures abo normal room temperatures, and whenusing acidic salts they should be those which hydrolize in solution to become sufliciently acid to catalyze the reaction with the cellulose. Preferably the ionization constant of the catalyst, when an acid, should be about equal to or greater than that of oxalic acid which is 3.8 10 The amount of catalyst necessary to give the desired degree of stabilization, will vary with the particular catalyst employed, and the catalyst selected should be one which, in the solution, will not produce a color on the textile material which is objectionable. Among these catalysts which are suitable may be particularly mentioned, as specific examples, the following: aluminum chloride (AlCls), stannic chloride (SnCh), zinc nitrate (ZnNOa), hydrochloric acid (HCl), malic acid (an unsaturated organic acid when used with other catalysts as a complex), calcium chloride (CaClz), zirconium oxychloride (ZrOC12), magnesium sulfate (in hydrate form such as epsom salts) and complexes of aluminum chloride and stannic chloride. At the present time, it appears that the aluminum chloride is the preferred catalyst for many fabrics but hydrochloric acid is also a very effective catalyst, as are complexes of aluminum chloride and stannic chloride which also give very excellent results. The acidic catalysts are all water soluble and may be used singly or together, depending upon the results desired.

The selection of the catalyst also determines to some extent the character of the hand of the textile material so treated and stabilized. Some of the acid catalysts give substantial discoloration of the textile material with varying shrinkage control, but with a catalyst such as aluminum chloride, stannic chloride, zinc nitrate, complexes of these, or malic acid, for example, the discoloration was minimized or eliminated and the shrinkage control became satisfactory. With other factors remaining constant, a change in the catalyst produced changes in the hand of the material. For example, the stannic chloride used with the glyoxal and amide reaction-product gave a definitely resinous hand to the treated textile material, but when the same reaction product of the glyoxal and amide was catalyzed with aluminum chloride, a relatively soft hand of the textile material was obtained. Each complex catalyst also gave a different hand than either of the components of that complex used separately, and by making various combinations or complexes of the catalysts, variations in the hand of the textile material may be obtained.

Depending upon the concentration or the ratio of the amide to glyoxal, the pH of the reaction product of the amide and the glyoxal may vary considerably. For example, the preferred ratio of formamide to the glyoxal may produce a reaction product having a pH varying from about 0.5 to 5.5. Changes in the catalyst used also produced a substantial variation in the pH of the treating bath which was less than about 4.5 and preferably between about 1 and 4.2. When employing formamide with the glyoxal to form a reaction product, we have found that as the concentration of the formamide in the'mixture is increased, the problem of discoloration on the textile material wetted thereby increases, apparently because of the uncombined amide in the solution.

The reaction between the textile material and the catalyzed reaction product of the glyoxal and amide may be caused either with or without a special'curing operation, depending somewhat on the concentration of the catalyst employed. It is preferable to carry outthe reaction between the textile material and the treating bath at the lower temperatures without a curing operation, because danger of discoloration is lessened to a marked degree at the lower temperatures. For practical reasons, it is usually preferable to dry the textile material, that has been wetted with this catalyzed reaction product of the glyoxal and amide, at temperatures well above room temperature, because otherwise it would be necessary to allow the wetted material to stand for relatively long periods of time in order to dry it and obtain the reaction with the cellulose of the textile material. A little heat to raise the temperature well above normal room temperature substantially accelerates the reaction of the catalyzed solution or bath with the cellulose, and thus decreases the time required for the treatment to practical periods.

The temperature usually need not be raised above-about 212 F., because very satisfactory results without objectionable discoloration have been obtained when the drying occurred at 212 F. or somewhat below. The temperature at which the wetted textile material is subjected in drying may, for example, be as high as 300 F. or more, but a temperature above 212 F. is usually of no advantage except to speed the drying for the reason that until the moisture is largely eliminated the temperature of the textile material itself will not exceed the boiling point of the wetting agent. At the start of the drying operation the temperature of the wetted material will not rise substantially above 212 F., but it may increase somewhat as the drying proceeds and the concentration of the reaction solution increases, with resultant increase in its boiling point.

The reaction may be carried on either with or without a curing operation, depending upon the concentration of the catalyst employed. If a suificient quantity of the catalyst is included in the solution used to wet the textile materials, the mere act of drying the wetted textile materials at a temperature well above room temperatures, but not materially above about 212 F., serves to cause the reaction between the cellulose and the reaction product of the glyoxal and amide. The same reaction between the cellulose and the reaction product of the glyoxal and the amide may be obtained with a considerably lesser amount of catalyst in the treating solution, if the treated textile materials, after drying, are subjected to a temperature above about 212 F., such as up to about 400 F. The time of curing, when the curing operation subsequent to drying is performed, depends upon the concentration of catalyst used and the temperature. The time is inversely related to the temperature and, for one example with one concentration of catalyst, was 3 minutes treatment at 250 F. in order to insure a complete reaction with the cellulose. When no curing operation is performed, the drying should occur well above room temperature, and should be continued until the treated textile materials are substantially bone dry, otherwise the reaction with the cellulose will be incomplete.

The following examples are given to illustrate more particularly the procedure and results obtained in practical application of this discovery, but it is to be understood that these examples are for illustration purposes only and are not to be considered as necessarily limiting the scope of the discovery or invention.

A 100% viscose. spun rayon 2 x1 right handed twill fabric in -the grelge was desized, boiled 01! and dried on a tenter frame. The white, pure finished fabrichadacountof134x62anda weight of 4.5 oz. per square yard. This fabric was then passed through an aqueous impregnatglyoxal-amide (acetamide) reaction solution and catalyzed with grams of aluminum chloride- 10 grams stannic chloride complex, with a pH of about 1.0 as made up. The molar ratio of aldehyde -to amide in thissolution was 1.85 to 2.22. After the fabric was well wetted out it was squeezed to remove solution in excess of 110% pickup. and was then dried on a pin tenter frame in air at around 220 degrees F., to the dimensions that the fabric possessed prior to impregnating. The dried, tentered fabric was then cured in oil'- culating air at 250 degrees F. for three minutes. The fabric, after curing. was removed from the pin-frame and subjected to three successive standard (CCC-T-191a) cotton wash tests for shrinkage. In the above procedure, no shrinkage is permitted during the process so that the residual shrinkage in the wash tests is a measure of the effectiveness of the process. A comparison of the shrinkage of the untreated and of the treated fabric is shown below. The tensile strength and the abrasion resistance of the fabric were not appreciably affected by the process.

Warp shrinkage on washings [Standard CCG-T-lQla Cotton Wash test, in inches per yard] Tensile strength Abrasion, Rev.

2nd Wash wash Wet w. F. w. F.

EXAMPLE #2 A plain weave, 100% filament viscosetafleta rayon fabric in the greige was desized, boiled oft,

ascarcr ,ingsolution containing, per liter, 250 cc. of the I and dried on a tenter frame. The white, pure finished fabric had a count of 77 x 58 and a a weight of 2.7 oz. per square yard. The fabric was then passed through an aqueous impregnating solution containing, per liter of bath, 250 cc. of

the glyoxal-amide (formamide) solution and catalyzed with 25 grams of aluminum chloride. The molar ratio of glyoxal to amide in this solution was 1.85 to 2.22. The bath had a pH of 2.1.

,After the fabric was passed through this solution and was well wetted out (requiring about 8 sec. immersion) it was squeezed to remove solution in excess of 100% pick-up, and then dried on a pintenter frame in air at around 212 degrees F. to the dimensions that the fabric possessed before impregnating. The dried, tentered fabric was then cured in circulating air at 250 degrees F. for

Warp shrinkage on washing: sm OOO-T-lilia Cotton Wash test, in inches per yard.]

Tensile strength 1 Abra- 1st 2nd 3rd Wash Wash Wash V- w. r. w. r.

Untreated. 1.8 2.2 -2.2 6! 30 24 17 200 m. .5 .5 4411352511 mo EXAMPLE #3 The fabric employed in this example was the same as the starting fabric employed in Example 1. This fabric was passed through an aqueous impregnating solution containing. per liter of bath, 250 cc. of the glyoxal-amide (formamide) reaction product or solution, catalyzed with 30 grams of aluminum chloride. The molar ratio of glyoxal to amide in this solution-was 1.85 to 2.22. The bath so prepared had a pH of 2.0 as made up. After the fabric was well wetted out. it was squeezed to remove solution in excess of about pickup and was then completely dried on a pin-tenter frame in air at around 220 degrees F. This treatment does not require an additional curing operation. The fabric, which is necessarily bone dry, was then removed from the pin-frame and subjected to three standard CCC-T-lQla cotton shrinkage washes forshrinkage. In the above procedure, no shrinkage is permitted during the process, so that the residual shrinkage in the wash tests is a measure oi. the effectiveness of the process. A comparison of the shrinkage of the untreated and of the treated fabric is shown below. The tensile strength and the abrasion resistance of the fabric were not appreciably aiiected by the process.

Warp shrinkage on washings [Standard CCO-T-lQla Cotton Wash test, in inches per yard] v Tensile strength 1 Abra 1st 2nd 3rd Wash Wash Wash wet i? 6V. t w. F. w. F.

Untle8h3d 4.9 4.8 4.9 81 43 5a 24 400 Treated 1.9 1.9 1.9 s5 s9 41 22 250 EXAMPLE #4 A plain weave, viscose rayon, challis fabric in the greige, made of 28/1 warp and 14/1 filling yarns was desized, boiled off and dried on a tenter frame. The white, pure finished fabric had a count of 66 x 41 and a weight of four ounces per yard. This fabric was then passed through an aqueous impregnating solution containing, per liter of bath, 250 cc. glyoxal-amide (acetamide) reaction product and catalyzed with a combination of 20 grams aluminum chloride and 10 grams zinc nitrate, with apH of approximately 1.0. The molar ratio ofglyoxal to amide in this solution was 1.85 to 1.7. After the fabric was passed through this bath or solution and was well wetted out, it was squeezed to remove solution in excess of about pickup and then dried on a p ltenter frame in air at about 220 degrees F., until it was about bone dry. This treatment did not require an additional curing operation. The fabric, after being dried in this manner was removed from the pin-frame and subjected to three standard CCCT19la' standard cotton wash tests 7 for shrinkage. In the above procedure, no shrinkage was permitted during the procesrmso that the residual shrinkage in the wash tests is a measure of the effectiveness of the process. A comparison of the shrinkage of the untreated and of the treated fabric is shown below. The tensile strength and the abrasion resistance of the fabric were not appreciably aflected by the process.

Warp shrinkage on washing A plain weave, viscose-acetate fabric having an all filament acetate warp, and a filament viscose filling in the greige was deslzed, boiled and dried on a' tenter frame. The white, pure finished fabric had a count 156 x 104 and a weight of 2.8 oz. per square yard. The fabric was then passed through an aqueous impregnating solution containing, per liter of bath, 250 cc. of the glyoxal-amide (acetamide) reaction product solution and catalyzed with a combination of grams aluminum chloride'=l 0 grams stannic chloride, with a pH of about 1.0 as made up. The molar ratio of glyoxal to amide in this solution was 1.85 to 1.7. After the fabric was passed throughthis solution and was well wetted out (requiring about 8 sec. immersion) it was squeezed to remove solution in excess of about 110% pick-up and then dried on a pintenter frame in air at around 212 degrees F. to the dimensions that the fabric possessed before impregnating and until the treated fabric was approximately bone dry. This treatment does not require an additional curing operation. The dried fabric was then removed from the pin-frame and subjected to three standard CCC-T-191a cotton shrinkage washes for shrinkage. 1n the above procedure the wetted fabric was returned to its original dimensions and so held during drying so that no shrinkage was permitted during the drying step, and hence the residual shrinkage in the wash tests is a measure of the effectiveness of the process. A comparison of the shrinkage of the treated and untreated fabric is shown below. The tensile strength and the abrasion resistance of the fabric were not appreciably afiected by the process.

Warp shrinkage on washing In the foregoing examples the warp shrinkage for the treated fabric indicates the effectiveness of the treatment as to progressive shrinkage, but the shrinkage figures given include the relaxation shrinkage or finishing loss as Well as residual shrinkage. This finishing loss is usually taken in the usual washing and slack drying that follows the chemical treatment in commercial practice.

For stabilization against shrinkage, an aqueous solution containing at least 77 cc. (preferably about 250 cc.) of the glyoxalamide reaction product is employed per liter of treating bath. When greater crease resistance and firmness of hand are required the amount of this solution may advantageously be increased to 400 cc. or more of this reaction product per liter of treating bath. A typical bath that gives excellent stabilization against shrinkage and substantially increases the bodyas wellas crease resistance of the treated textile material includes from 150 to 250 cc. of the glyoxal-amide reaction product per liter of bath.

The amount of the acidic catalyst per liter of treating bath should be suflicient to produce the desired or maximum stability of the treated textile materials, and usually at least 3 grams of catalyst per liter of bath is necessary. The maximum amount of. catalyst is not sharply critical, but if too much catalyst is employed there is danger of damage to the textile material. One should, therefore, employ just that minimum amount of catalyst which gives the desired results only, thus avoiding unnecessary danger of damage to the textile materials so treated and avoiding waste of the catalyst. The amount of catalyst also depends on the activity of the catalyst employed. Up to grams of malic acid in a complex per liter of treating bath have been used successfullly.

The drying temperature is preferably below about 212 F., but well above normal room temperature, with the drying continued until the treated textile materials are approximately bone dry where no additional curing is desired. Where the textile materials are to be cured in a subsequent step, the drying need not necessarily be continued until the treated materials are bone dry, but the drying is preferably continued until the textile materials have the appearance of approximate dryness.

The baking or curing temperature which is required when a relatively low concentration of catalyst is used, is above about 212 F. and preferably from about 250 F. to 300 F. The maximum temperature is not sharply critical, but since high temperatures may possibly be injurious to the treated textile materials, it is advisable to keep the temperature relatively low, but within .the curing range, to avoid danger of damage to the materials.

The baking or curing time is inversely related to the temperature and depends also upon the activity and concentration of the particular catalyst which is employed. The curing should continue until the stabilization has been substantially effected, but subjecting the treated materials to further curin than necessary is inadvisable in order to avoid danger of damage to the treated textile materials through exposure to the curing temperature.

This discovery is not recommended for textile materials containing large amounts of cotton, for the reason that the treating bath is strongly acid, and acids are likely to adversely affect the physical properties of the cotton and damage it. This discovery is also not recommended for W001 or protein rayons because of discoloration generally imparted to the fabrics. It is practical for blends of viscose and acetate rayons.

' grams (by weight) of the acetamide.

In preparing the reaction product of glyoxal and amide, the best results so far havebeen obtained by employing equal molar proportions of glyoxal and amide, such as about 359 to 360 grams by weight of a 30% (byweight) commercial aqueous solution of glyoxal with about 114:0

e formamide is somewhat more active in this reaction with the glyoxal than is the acetamide.- The maximum proportion ofthe glyoxal and the amide which is believed can be safely used without danger or objectionable discoloration of the treated textile materials, and without damage to the textile materials, is about 1 mole of glyoxal to 8.3 molesof the amide, such as, for example, about 350 grams (by weight) of the commercial 30% (by weight) solution of glyoxal with about 200 grams ofacetamide. The minimum proportion which it is believed one can use and obtain reasonably satisfactory stabilization results is about 1 mole of glyoxal with each mole of amide, such as, for example about 350 grams (by weight) of the commercial 30% (by weight) glyoxal solution with about grams '(by weight) acetamide. Quite often smaller quantities of the amide have been used with fair success, particularly with the higher amides. If less than about 25 grams of formamide or the acetamide is used for example, it is possible to obtain the requisite stabilization, but because of the large amount of unreacted glyoxal remain ing in the solution the damage to the textile materials may be objectionably high. i

10 moles of amide, and anacidic catalyst. the acidic component ofwhich increases in acidity and is not eliminated when concentrated to approximate dryness, the pH of the treating solution being less than about 4.5, removing excess wetting solution, and drying and curing said wetted materials that have been freed of excess solution. a

2. The method of stabilizing, against progressive dimensional shrinkage under repeated washings, a textile material containing predominantly regenerated cellulose and substantially free of wool and protein fibers which comprises wetting said material with an aqueous solution of the reaction product of molar quantities of glyoxal and an amide having the formula BALM.

where R represents a member of the group consisting of hydrogen and an alkyl radical havin; less than a four carbon atom primary chain,

cess wetting solution, and drying and curing said One may also employ methyl glyoxal in place uct with the cellulose, thus providing a more permanent effect than can be obtained by the use of formaldehyde, and the product is characterized, we believe, by less relative slippage of the molecular chains, so that the material is more resistant to crushing and creasing than the non-treated material or one that has been treated with formaldehyde or compounds thereof. Methyl glyoxal, therefore, we consider to bean equivalent of regular glyoxal, within the broadest scope of the discovery, and both methyl glyoxal and regular glyoxal may be identified as aliphatic dicarbonylic compounds.

We claim:

1. The method of stabilizing, against progressive dimensional shrinkage under repeated washings, a textile material containing predomoninantly regenerated cellulose and substantially free of wool and protein fibers which comprises wetting said material with an aqueous solution of the reaction product of glyoxal and an amide having the formula R-Hl-NH:

where R represents a member of the group consisting of hydrogen and an alkyl radical havin less than a four carbon ,atom primary chain, the molar ratio of glyoxal to amide in the solution being 1 mole of glyoxal to not less than about )4; mole, and not more than about 3.3

wetted materials that have been freed of excess solution. 3. The method of stabilizing, against progressive dimensional shrinkage under repeated washings, a textile material containing predominantly regenerated cellulose and substantially free of wool and protein fibers, which comprises wetting said material with an aqueous solution containing between 75 cc. and 400 cc. per liter of the reaction product of glyoxal and an amid having the formula 0 R-LNH: I; where R represents a member of "the group consisting of hydrogen and an alkyl radical having less than a four carbon atom primary chain, the -mo1ar ratio of glyoxal to amide in the solution' being between mole and 3.3 moles of amide for each mole ofglyoxal and an acidic catalyst the acidic component of which increases in acidity and is not eliminated when concentrated to approximate dryness, the pH of the treating soe lution being less than about 4.5. removing excess wetting solution, drying said wetted materials that have been freed of excess solution at a temperature well above normal room temperature, and then curing the dried materials.

4. The method of stabilizing, against progressive dimensional shrinkage under repeated washings, a textile material containing predominantly regenerated cellulose and free of wool and protein fibers, which comprises wetting said material with an aqueous solution containing between 75 cc. and 400 cc. per liter of the reaction product of molar quantities of glyoxal and an amide having the formula 0 raiser.

where R represents a member of the group con sisting of hydrogen and an alkyl radical having less than a'four carbon atom primary chain, and an acidic catalyst having an ionizationconstant of not less than about 3.8X10- 25 C. and the acidic component of which catalyst increases in acidity and is not eliminated when concentrated to approximate dryness, the pH of the treating solution being less than about 4.5, removing excess wetting solution, drying said wetted materials that have been freed of excess solution at a temperature well above normal room temperature, and then curing the dried materials.

5. The method of stabilizing, against progressive dimensional shrinkage under repeated washings, a textile material containing predominantly regenerated cellulose and free of wool and protein fibers, which comprises wettin said material with an aqueous solution containing between '75 cc. and 400 cc. per liter of the reaction product of glyoxal and an amide having the formula where R represents a member of the group consisting of hydrogen and an alkyl radical having less than a four carbon atom primary chain, and

in which the glyoxal is used in the proportions between about 350 gms. by weight of 30% by weight aqueous glyoxal solution to a minimum of about 25 gms. by weight and a maximum of about 200 gms. by weight of the amide, and an acidic catalyst having an ionization constant of not less than about 3.8X- 25 C. and the acidic component of which catalyst increases in acidity and is not eliminated when concentrated to approximate dryness, the pH of the treating solution being less than about 4.5, removin excess wetting solution, and drying and curing said wetted materials that have been freed of excess solution 6. The method of stabilizing, against progressive dimensional shrinkage under repeated washings, a textile material containing predominantly regenerated cellulose substantially free of wool and protein fibers, which comprises wetting said material with an aqueous solution containing between 75 cc. and 400 cc. per liter of the reaction product of glyoxal and an amide having the formula where R represents a member of the group consisting of hydrogen and an alkyl radical having less than a four carbon atom primary chain, the solution containing from about 2; mole to 3.3 moles of amide for each mole of glyoxal and an acidic catalyst complex containing aluminum chloride and stannic chloride, the pH of the treating solution being less than about 4.5, removing excess wetting solution, and drying and curing said wetted materials that have been freed of excess solution.

7. The method of stabilizing, against progressive dimensional shrinkage under repeated washings, a textile material containing predominantly regenerated cellulose substantially free of wool and protein fibers, which comprises wetting said material with an aqueous solution containing between 75 cc. and 400 cc. per liter of the reaction product of glyoxal and an amide having the formula where R represents a member of the group consisting of hydrogen and an alkyl radical having less than a four carbon atom primary chain, the solution containing from about mole to 3.3 moles of amide for each mole of glyoxal and an 12 acidic catalyst containing aluminum chloride, removing excess wetting solution, the pH of the treating solution being less than about 4.5, and drying and curing said wetted materials that have been freed of excess solution.

8. The method of stabilizing, against progressive dimensional shrinkage under repeated washings, a textile material containing predominantly regenerated cellulose substantially free of wool and protein fibers, which comprises wetting said material with an aqueous solution containing between 75 cc. and 400 cc. per liter of the reaction product of glyoxal and an amide having the formula where R represents a member of the group consisting of hydrogen and an alkyl radical having less than a four carbon atom primary chain, the solution containing from about mole to 3.3 moles of amide for each mole of glyoxal and an acidic catalyst having an ionization constant of 'not less than about 3.8x10- 25 C. and the acidic component of which solution increases in acidity and is not eliminated when concentrated to approximate dryness, the pH of the treating bath being less than about 4.5, removing excess wetting solution, and drying and curing said wetted materials that have been freed of excess solution.

9. The method of stabilizing, against progressive dimensional shrinkage under repeated washings, a textile material containing predominantly regenerated cellulose substantially free of wool and protein fibers, which comprises wetting said material with an aqueous solution containing between 75 cc. and 400 cc. per liter of the reaction product of glyoxal and an amide having the formula where R represents a member of the group consisting of hydrogen and an alkyl radical having less than a four carbon atom primary chain, the solution containing from about mole to 3.3 moles of amide for each mole of glyoxal and an acidic catalyst the acidic component of which increases in acidity and is not eliminated when concentrated to approximate dryness, and which hydrolizes to give a solution sufliciently acid to catalyze the reaction with said material, the pH of the treating solution being less than about 4.5, removing excess wetting solution, and drying and curing said wetted materials that have been freed of excess solution.

10. The method of stabilizing, against progressive dimensional shrinkage under repeated washings, a textile material predominantly of regenerated cellulose substantially free of wool and protein fibers, which comprises wetting said material with an aqueous solution of the reaction product of glyoxal and an amide having the formula 0 R--NH:

where R represents a member of the group consisting of hydrogen and an alkyl radical having less than a four carbon atom primary chain, the solution containing from about mole to 3.3

moles of amide for each mole of glyoxal and an acidic catalyst having an ionization constant of not less than about 3.8 l0- 25 C., and the acidic component of which solution increases in acidity and is not eliminated when concentrated to approximate dryness, the pH of the treating action product of glyoxal and an amide having.

the formula R-H NH where R represents a member of the group consisting of hydrogen and an alkyl radical having less than a four carbon atom primary chain, the solution containing from about mole to 3.3 moles .of amide for each mole of glyoxal and an acidic catalyst having an ionization constant of not less than about 3.8 C. and the acidic component of which solution increases in acidity and is not eliminated when concentrated to approximate dryness, the pH of the treatin solution being less than about 4.5, removing excess wetting solution, and drying and curing said wetted materials that .have been freed of excess solution. v

12. The method of stabilizing, against'progressive dimensional shrinkage under repeated washings, a textile material of a blend of regenerated cellulose and acetate rayon, with the regenerated cellulose predominant which comprises wetting said material with an aqueous solution of the reaction product of glyoxal and an amide having the formula where R represents a member of the group consisting of hydrogen and an alkyl radical havin less than a four carbon atom primary chain, the solution containing from about mole to 3.3 moles of amide for each mole of glyoxal and an acidic catalyst the acidic component of which solution increases in acidity and is not eliminated when concentrated to approximate dryness, and which hydrolizes to give a solution sufliciently acid to catalyze the reaction with said material, the pH of the treating bath being less than about 4.5, removing excess wetting solution, and drying and curing said wetted materials that have been freed of excess solution.

13. The method of stabilizing, against progressive-dimensional shrinkage under repeated washings, a textile material of a blend of regenerated cellulose predominant which comprises wetting said material with an aqueous solution containing between 75 cc. and 400 cc. per liter oi! the reaction product of glyoxal and anamide havin the formula cellulose and acetate rayon, with the regenerated 14 to approximate dryness. the pH of the treating bath being less than about 4.5, removing excess wetting solution, and drying and curing said wetted materials that have been freed of excess solution.

14. The method of stabilizing, against progressive dimensional shrinkage under repeated washings, a textile material containing predominantly regenerated cellulose and substantially free of wool and protein fibers, which comprises wetting said material with an aqueous solution of the reaction product of an amide having the formula where R represents hydrogen or an alkyl radical having less than a four carbon atom primary chain, with an aliphatic dicarbonylic aldehyde of the group consisting of glyoxal and methyl glyoxal, in which reactionproduct the ratio of aldehyde to amide is between about 1 mole aldehyde to each 3.3 moles of amide and about 1 mole of aldehyde to each mole of amide, and an acidic catalyst, the acidic component of which has an ionization constant of not less than about 3.8 10-/", 25 C. and'wliich component increases in acidity and is not eliminated when concentrated to approximate dryness, the pH of the treating solution being less than about 4.5, removing excess wetting solution, and drying and curing said wetted materials that have been freed of excess solution.

15. The method of stabilizing, against progressive dimensional shrinkage under repeated washings, a textile material containing predominantly regenerated cellulose and substantially free of wool and protein fibers, which comprises wetting said material with an aqueous solution containing the reaction product 01' an amide having the formula where It represents a member oi! the group consisting of hydrogen and an alkyl radical having less than a four carbon atom primary chain with an aliphatic dicarbonylic compound of the group JACK EPELBERG. RAYMOND E. PEMRICK.

REFERENCES CITED The following reierences are of record in the flle of this patent:

UNITED srwrns PATENTS Number Name Date 2,165,265 Hubert et al. July 11, 1989 2,211,976 Hubert et al. Aug. 20, 1940 2,242,051 Beck May 13, 1941 FOREIGN PATENTS Number Country Date Ml Great Britain Mil. 4, 1036 

1. THE METHOD OF STABILIZING, AGAINST PROGRESSIVE DIMENSIONAL SHRINKAGE UNDER REPEATEDLY WASHINGS, A TEXTILE MATERIAL CONTAINING PREDOMINANTLY REGENERATED CELLULOSE AND SUBSTANTIALLY FREE OF WOOL AND PROTEIN FIBERS WHICH COMPRISES WETTING SAID MATERIAL WITH AN AQUEOUS SOLUTION OF THE REACTION PRODUCT OF GLYOXAL AND AN AMIDE HAVING THE FORMULA 